Production of valuable hydrocarbons from carbonaceous materials, tars, mineral oils, nd the like



PRODUCTION OF VALUABLE HYDROCARBONS FROM CARBONACEOUS MATERIALS, TARS,MINERAL OILS, AND,THE LIKE Original Filed Nov. 20, 1928 Dec. 6, 1932. vM, PIER 1, 90,437

I ontoz 77Za'b71ias Pier" 35%713 mime 1 I Recycle Pam c Patented Dec. 6,1932 U ITED I TATES,

PATENT- oFFIcE KATHIAS PIER, OF KEIDELBEBG, GERMANY,'ASSIGNOR, BY MESNEASSIGNMENTS, TO

'sr'ANnm-I'. e. comm, or LINDEN, new man, A coarosarron or Dam f -summonpr 'vALoaBLE mnocmons anon 'cannonacnous mammal TABS, MINERAL OILS, ANDTHE LIKE Application filed November at), 1928, Serial No. 820,764, andin Germany November 24, 1927. Renewed Kay 12, 1932. I I

Valuable products containing 1 liquid hydrocarbons obtained fromvariousikinds of coal, tars, mineral oils andgthe like have' hithertobeen roduced by treatment of the same with" hy rogen or gases supplyingthe same at elevated temperatures and pressures in a'single reaction"vessel;v A process-has also already been suggested according to whichthe products obtained, from one vessel, forexamp e in the form of;vapor, are.cata

lytically treated in a secondreaction vessel -arranged behind the first,r

I have now found, that the. destructivehydrogenationjof carbonaceousmaterials fsuch as the various kinds of jcoa1,tars,jlm1ne'ra1 ;oils-andthe like, especiallyas regards {the consumption 'of energy and thesimplification of the entire operation, may. be carried out in anadvanta eous mannerby conducting the products w ich; are to be treatedtogether with hydrogen through" more than'two reaction. vesse s arran edonebehind the other in such a manner tlat no appreciableqcooling occursbetween the vanousreact onvesselsh f v The avoidance of appreciableeoohngxbetween the .various reaction vessels 1s effected,

for example, by making the connections between the separate reactionvessels veryshort or by employing a high'rate' of flow of the materialsunder treatment or by surrounding the connections, and, if desired, thereaction vessels with atjacket of a heatingmedium flowing inaspecialcirele or by any of these.

means combined. Small quantities of gas medium. a I Inaccordance withthe; present mventlon extremely large charges may I and far less gas isneeded than would be the easewith the same charge in ve'ssels arrangedsingly or in parallel formation; mostsuitably the gas. is repeatedlyused in a circular t In consequence of thed e/a;

are suflicient for the employment as a'heatingbe employed.

tity of gas in contrast' with the usual proc--" esses, theenergyrecovered in the regener'a tors is greatly increased, because, thesmaller the total quantity of gas passing through the Iregenerator thesmallerare the losses. heat.

he replacement of the-10 heatre- Moreover, t I I y generators which-would be used with, 10

with the present invention, isof considerable from one'largeregenerator, whilst it"is also common knowledge that'largeun'itsare much more'economical than small units..,

The preheating of the materialsi tow be treated and of the hydrogenatinggases may H be carriedout in the regenerators' and/Orin specialpreheaters, which arepreferabl '3 not heated throughrthe walls whicharesu jectfi'ntage, since the 11eat,, I10 small regenerators is mu h rthan ed to pressure, in cases whenthe materials are preheatedunder:pressure. The production of heat in the preheatersjrnay becarried out,for example, by means'of electric'alresistance heating. 'l he preheatersmay also slmplycontain a heating medium, for examle gases or vapors ofany composition which ave been heated, and which in turn'heat thematerials which take part in the reaction a. to the necessarytemperature. Wh'enthe plant reactiong; I I It is possible to convey heatfrom-onereaction vessel 'to another by suitable choice of 75 is inoperation, the preheater may, if desired, be partially orentirelyeliminated, according to the efiiciency of th e heat toneoi thethe velocity of flow of the reacting -components and in thismannerfluctuations 'in temperature and undesirable excessivelocalheating may be avoided, and an equalizatlon of heat betweenitheseparate reaction vessels maybebrou'g'htabout. v I

Fluctuations in thereaction temperature,

. to which the destructive hydrogsengtion price; 0 e'avoi e esses arevery sensitive, may a v if desired,

by employing a heating medium which is passed in a special cycle. lforthis purpose comparatively small quantities of gas are suflicient whichagain means an economy in energy.

As regards the attention required in the operation this process is verysimple, since, it is only necessary to have an inlet for the initialmaterials and an outlet for the products. The removal of the F651- duesis also greatly simplified, because thesemay be passed to a place,

out or for the purpose of regenerating the the state of liquid or vapor,

catalyst, or for interchanging them with an auxiliary reaction vessel,without interruption of the process as a' whole.

The hydrogenating gases are preferably introduced together with thematerials to be distribution and the intimate treated. The mixing of thehydrogenating gases with the materials to be treated is effected byemploying high speed linear currents, by which injurious localdeposition or thickening is simultaneously avoided. Generally speaking,

it is not necessary to employ special stirring 'ap aratus.

he amount of pressure and the linear velocit of 'the stream are sochosen that there is still an excess of hydrogen in the last reactionvessel. a

The joints between the separate reaction vessels. are preferably made,short so that losses of heat are reduced to a minimum.

The initial materials may be employed in and materials of the nature ofcoal are preferably treated presence of catalysts,

in the form of suspensions. In cases where a residue is produced, it ispreferable to ar-. range that all the liquid products are not distilledoff, but that a suflicient quantity of the same remains behind tofacilitate the removal of the residue.-- Before separating the hydrogenfrom the liquid products leaving the reaction vessel, the mixture ispreferably cooled, in order to prevent injury to the conduitsbydeposition. a

The operation may be carried out in the and in cases where these areemployed in the form of s uspensions they may be returnedto thereactionWhen working with moving hot liquid, for example,-dispersed in a finelydivided or colloidally dissolved state examplemetallic sulfids,

or in a state of suspension in a current of the gas. All those catalystssuitable for the art' of destructive hydrogenation may be employed, inparticular those immune to poisoningb sulfur.

ble or the purposes of the present invention may be mentioned catalystscomprising compounds containing s'ulfur in combination, for inparticular the heavy metal sulfids and more especially those of the irongroup, either alone or as mixtures with one another or with metals,metalloids, active charcoal, coke or the like or with -oxids, hydroxids,or carbonates or with other materials of a catalytic or of inert nature.The sulfur may also be combined with the catalyst by adding sulfites orsulfates thereto or by the addition of sulfur to metals or oxids. A verysuitable catalyst may be obtained by treating iron with hydrogen sulfidat .an elevated temperature; Particularly suitable catalysts of thisclass are, for example, cobalt sulfid, iron sulfid, zinc sulfid, nickelsulfid, manganese sulfid and the like or mixtures thereof, for example,mixtures of cobalt sulfid with nickel sulfid or of cobalt sulfid withmanganese sulfid, or of cobalt sulfid mixed with iron sulfid, or withzinc sulfid or w th aluminium oxid, with or without an addition of inertsubstances. Catalysts consisting of or containing a metal of the 6thgroup-of the periodic system, such as molybdenum, chromium, tungsten oruranium or the compounds thereof or mixtures of these substances arealso particularly-suitable. As examples of this type of catalysts may bementioned molybdic acid or ammonium molybdate, tungsten sulfid, tungsticacid, chromium hydroxid and chromic acid. Mixtures of chromium ortungsten with other catalysts, such as with cobalt, nickel or iron Asexamples of catalysts suitmay also be employed.- Activation of thecatalysts or the addition of substances increasing their mechanicalstrength may also be of advantage, this being efi'ected for example withsubstances having a basic action, 4

such as potassium carbonate, droxid or calcium carbonate: aslumps ofaluminium silicate may also be employed with advantage. As furthercatalysts may be mentioned oxidic catalystscomprising zinc oxid,chromium oxidor manganese oxid or mixtures of these, with an addition ofa compound containing fixed nitrogen, such as ammonium sulfid orsuchvnitrids as are comparatively stable against the action of water,for example silicon nitrid or titanium nitrid. These said oxidiccatalysts may be employed in conjunc- Carriers, such tion with othersubstances, such as lumps of fire-clay, quartz, asbestos, pumice, coke.ac-

tive charcoal, metals, in particular heavy metals, metalloids, oxids,sulfids, carbids, and the like and'mixtures thereof with the saidsubstances. As still further examples of aluminifim by:

if desired,

I suitable catalysts may be mentioned, such containing at least one ofthe elements silver, .copper, cadmium, lead, fbismuth, tin in the formof its compounds, further thediflicultly reducible metal oxids orcarbonates, such as magnesia, lithium carbonate, boric' acid, alumina,the rare earthsincluding the diflic'ultly reducible oxids of-metals fromthe 4th group of the periodic system, or the oxids of zinc, manganese orvanadium.v The catalysts may contain several of these substances or alsoother substances,'for example metals from the 8th group of the periodicsystem, such as iron. As, specific examples of these catalysts may bementioned such obtained by impregnating porous refractory materials withsolutions of lead nitrate, or ofstannous chlorid, silver nitrate or ofcopper hydroxid, either aloneor in admixture with compounds of iron,cobalt and the like. Fu'rther may be mentioned catalystscontaining theoxide of silver or of titanium, orzlithium carbonate, magnesite,manganous oxid, silver borate or mixturesof copper oxid with cerous,oxidor of silver with. cobalt oxid. and the like, and also porousrefractory masses: coated with vanadium oxid or thoriumoxid; or with amixture of compounds of. uranium andfzinc or of silver and tungsten."These latter compounds ,may also be employed as such; withoutapplication to the said porous materials.

As further suitable catalysts may be. mentioned catalysts. containingactive-charcoal or the metalloids boron, si-licon, .phosphorus,

arsenic, selenium, tellurium or the compounds thereof, orhalogens.:ThesemetaHoids may advantageously be employed together with elementsfrom the2ndto the 8th group ofthe periodic system, in particulansuchselected from the 6th group of" the periodic system. The catalystsmayffor example contain the followingacids or their salts, name- 1yphosphoric I acid,l arsenious acid, -silicic acid, boric acid,hydrofluoric'iacid,hydrochloric acid,selenious acid and they/like. Asspecific examples -mayfbe mentioned silicon carbid, alder-woodcharcoal-which ,has been glowed at 800 C. and impregnated withphosphoric acid, calcium pl1dsphate,,molybdenum phosphate,tungsten;phosphate, .i-ron phosphate, aluminium. phosphate, arseniousacid together with molybdenum or tungsten,

silioids, for example iron silicidqconta'ining 15.per cent of silicon,active silica, hydrosilicates, borids, such as titanium borid or IIOIL.bond, calclum fluor d, molybdenum with 10 per cent of aluminium chlorid,mo1ybdenum with 10 per cent of aluminium chlorid,

molybdenum with 10 percent of cadmium chlorid, molybdic acid with sodium"selenite.

Compounds containing fixed nitrogen may also, be employed withadvantagein the reaction. Thus ammonia .or its. salts, for; ,example,-ammonium sulfid and in some cases organic compounds of nitrogen may alsobe be mentioned suchjcontaining one or more,

found to give particularly good results. I As further examples ofsuitable catalystsmay elements from a (the 4th to the 8th group of theperiodic system, inpar ticular such from the 6th group of the periodicsystem and more particularly molybden'um) together with 6 (smallamountsof other elements from the 2nd to the 7thgroup of the periodic,system or copper or' gold or the compounds thereof). 7 The elements fromthe 2nd and 3rd group may however also be employed in large amounts. 1Thus mixtures containing molecular proportions of molybdic acid withmagnesia or with copper or with aluminium hydroxid, or mixturesoftungstic acid with zinc oxid or of vanadium oxid with magnesia furnishgood results. Excellent catalysts are furthermolybdic acid with about'10 per cent of chromium oxidyor of vanadium oxid, molybdic acid withabout 10 per cent of ura- Ilium oxidor of thorium oxid or-of'manganousoxid, further; tung stic acid containing about 10 per, centof chromiumoxid or of a mixture of uranium oxid, cobaltanda small amount ofchromiumoxid. ,Again "aniotherflvery suitable; class. of catalysts is ,fo rmedby the noble metals or lead ortin or compounds thereof on carriers,inparticular I on magnesia or magnesite or chromium oxid.

As examples of this class of catalystsnla-y be mentioned iruthenium,jpalladium, platinum,

old 'leadjo'r tin orma nesia or ma nesite 3 I a D, b-

;or platinum orgoldor chromiumoxid." Catalysts containing, smallamounts'of, silver :or

tion, and preferably also boron ,or alummlum or silicon or t tanium, orvanadium,

I or' tantalum or chromium or molybdenum or tungstenor cobalt in, streamcombined state or, mixtures of theselare also very suitableQfExamples ofsuchcatalysts .are' tantalic acid containing 10 per centof silver,

vmolybdic acid containing 10 percent of silveror silica containing 10per cent of a mix- 'ture of copper and z'inc. Again another. a

class of catalysts consistsoflrefractory met- 1 als or alloys on whichsmall amounts of solid bxids, of elements having, a catalytic actionifrom thel3rd to the 7th group of the periodic system havebeendepositedThe said met als or their alloys m1 preferablyemployed in an etchedcondition and. preferably acidified solutions: or salts llof ,the 1 saidoxids are employed as theet'ching agent.-

iao

The products may bekept in motion within :the separate, reactionvessels,-for example by imparting to the material under treatment such.an intensive statef of movement in all ,those par'ts;of-theapparatumwhere it is subje cted toheat treatment, that-noinjuriousu local thickening occurs, and ensuring a' good product undertreatment, the participants in the reaction being preferably admittedand removed in a continuous manner. This state of motion of the liquidmaterials under treatment may, for example, be set up by introducing thehydrogenating gas through numerous small apertures, for example throughperforated or sieve plates, which, if desired, are arranged in severallayers one above the other and/or through one or several nozzles, whichpreferably have the form ofejectors, under a pressure considerably inexcess of that prevailing in the reaction vessel, in such a manner thata continuous drawing up and a whirling motion of vortexcharacter is setup in the liquid materials, accompanied by a very thorough intermixingof the said materials with gas bubbles of smallest dimensions. In placeof or besides a high excess of pressure,a mechanical stirrer may beemployed, which, if desired, ma also be provided with apertures ornozzles or the introduction of hydrogenating gas.

The movement of the liquid products, with the object of preventinginjurious local thickening may also be suitably effected by circulatingthe liquid reaction materials in a hot state. This may be brought aboutby special mechanical appliances inside the reaction fur nace,'or alsoby conducting the liquid material out of the furnace and back into itagain.

In'the lattercase care must be taken to prej vent'any' cooling whichmight result in local deposition of thickened portio s. The circulationmay be produced by pumps of the -most 'varied' types, such asreciprocating pumps, valveless' pumps, for exam le geared pumps,centrifugal pumps and the ike. This method of working enablesthe rate'offlow to be greatly increased. Several liquid circuliltlOXlS may also beproduced simultaneously.

Under certain circumstances it is also of ad-' vantage to maintain a hotgas circulation, the

reaction products formed being separated ofi either periodically orcontinuously. If desired, products may be added moved from the separatereaction vessels, for

example at'an intermediate state of the re.- action. Ashes, residues'andthe like may also be removed from the se arate furnaces. The residuesmay also e removed together with the reaction product and the 200 oreven subsequent separation carried out in any known and suitable manner.

The process in accordance with the present invention is carried out withadvantage in vertical reaction vessels (towers), under an elevatedpressure, preferably above atmospheres. Pressures, for example of 50,100,

1000 atmospheres come into question depending on the. degree ofdestructive hydrogenation desired, higher pressures lead:

'ing to a more intensive treatment than lower pressures. However,in'some cases it will be turesl ing above the temperature,

velocity of throughput.

" preferable to employ to or re-I form of vapor, and in advantageous to'employ atmospheric pressure. The process is carried out attemperadecomposition temperature o the materials to be treated, butusually between about 300 and 700 C. Different temperatures may bemaintained in the var:0u's reaction vessels, for example 1n such amanner that the lnitlal materials are treated inseveral stages, bysubjecting the cons titue'its which are not affected or not appreciablyafiectedbyhthe first treatment to atreatment by themselves at a highertemperature than I, in the firststage of the destructive hydro-*"genation; Accordingly not the whole of the product obtained by the firsttreatment is subjected to a repeated treatment at a higher but theinitial materials are subjected to treatment at a definite temperature,preferably as low as possible owing to which only a part of thematerials is converted into valuable liquid substances. The unchangedremainder is separated and'partly, or wholly,

sub'ected to treatment with hydrogen at a hig er temperature than in thefirst stage of the treatment. Distinct fractions may also the highertemperature and may be worked up in anotherway, for example for thepreparationof lubricating oils and the like. In the first stage it ispreferable to employ a higher The height of the temperature. employed independs onthe nature of the initial on the conditions in lthe firsttreatment and on the nature of the products which are desired thus, forexample, if mainly aromatlc compounds are desired, temperatures of 500C. or more are employed and if the temperature in the first stage israther high, the temperature in the second stage must be correspondinglyhigher.

In some cases well defined products may be" obtained by the employmentof further stages with still higher temperatures. In the stage atrelatively high temperature, itis the materials in the hydrocarbons maychiefly be obtained, if desired.

The nature of the invention will be further illustrated by the followingexample with reference to the accompanying drawing, though it' .isunderstood that the invention is not limited to this particularmodification.

' Brown coal low-temperature tar containup to 325 C. and about 10 ,percent of asphaltum, is treated with by r pressure of'200 atmospheres in 5reaction vessels 1'-5 arranged in series, one or more of which can beshut out from the circulation be 00 "separated ofi before the furthertreatment at the second stage materials,

this manner aromatic I ing about 30 percent of constituents boilingogen. under a a 1 pump A. A pressure of about 200 atmos-' ucts may beremoved from the reactionvessel the vent E and V The initial materialsare reheated in the coiL C to a temperature of a out 410 C. They enterinto the reaction vessel,- 1 through the admission valve D by way of Aneiiluent pipe F is arranged in the base of the said vessel near Ethrough which the liquid reaction products formed can be drawn offthrough the valve G The initial materials pass upwards in thesaidreaction vessel 1 through the catalyst mass J consistingof'molybdenum trioxid and zinc oxid which is rigidly arrangedin thereaction vessel. The said reaction vessel is surcount of the positiveheat tone of the reaction,

the temperature of the materials treated in the reaction vessel 1 hasrisen to about 425 C.

and the said materials enter the second reac-- tion vessel with atemperature of about 420 C. The reaction vessel 2 and the followingreaction vessels 3'5 also'contain catalysts consisting of molybdenumtrioxid and zinc. oxid rigidly arranged therein. All parts of thereaction vessels 25 are arranged similarly to the arrangement in thereaction vessell and the correspondingparts are enumerated by the sameletters only bearing different numerals. At the upper end of thereaction vessel 2 the materials have a temperature of about 435 C. andthey enter the reaction vessel 3 with a temperature of about 430 C. Thetemperature rises from vessel to vessel by about 5 to C., so that theproducts leave the reaction vessel 5 with a temperature of about 450 to460: C. by means of the valve D They are passed through the condenser Minto a stripping vessel N in which the liquid products which have beencondensed collect at the bottom and are drawn off by means of the valveP. The gases pass on through a conduit tothe circulating pump Q. Part ofthe circulating gases which consist of gaseous hydrocarbons formed inthe course of the reaction may be drawn off through the valve 0- and maybe replenished by fresh gases introduced by means of the pheres ismaintained throughout the circulation. It is not necessary to remove theliquid reaction products from each of the reaction vessels, for examplepart of the reaction prod- 3while the rest is drawn off from thereaction ivessel 5. The products drawn off from the reaction vessel 3are practically free from asphaltum and when worked up for theproduction of lubricating oils yield a good enexcluded from thecirculation.

gineoil in anamount of about per cent' of the said products, theremainder consisting mainly of middle oils which are usually returned tothe process orwhich are separatelyworked u for the production ofbenzine. Mainly middle oils arealso" drawn 05 j from the reactionvessel- 5 by way of the valve G the li uid in the reaction vessel beingmaintained at a constant level. The vaporous products leaving thereaction vessel 5 together with-the ases which-are condensed in the coilM consist of benzine to the extent of about 50 per cent, the remainderbeing a light oil which may either-be employed as such or which may beconverted in a second destructive hydrogenation process into ben- 21m.

In order to regenerate theicatalyst in any .7

given reaction vessel the said vessel may be Thus, for example, if thereaction vessel 1 is to: be excluded from the circulation, the valve Dis closed, the circulating valve H is opened and the valve L closed. Thepressure in the re action vessel 1 is thereupon released. The

valves G, L and D are arranged as three-way cocks. The initial materialsto be subjected to the reaction then heating device C directly through HS and D into the reaction vessel 2. The liquid contents of the reactionvessel 1 are now removed through F and a valve Gr and air is blown intothe reaction vessel, which is still hot, by Way of the valve L or alsoin some cases a mixture of air and nitrogen, care being taken thatthetemperature does not rise above 500 C. during this process.

The valves and efiluent pipes are arranged somewhat difi'erently in thereaction vessel 5 from-the arrangement in the other reaction vessels,but when this vessel is to be excluded from the-circulation, the methodof working is exactly the same as in the case of the other vessels, airbeing blown in by means of the valves D and removed by means "ofG What Iclaim is 1. A process for producing liquid hydro pass by way of theprecarbons by destructive hydrogenation of carbonaceous materials in theliquid state which mospheres, the speed of flow of the materials.

and the temperature in at least the first two vessels of the seriesbeingsuch that the reac-. tion is only partially effected therein, all thevapors resu ing from-the treatment in at least said first two vesselsbeing passed, through all the remaining vessels of the series whileavoiding appreciable cooling in the flow of materials from one vessel toan-- other. i I 2. A process as defined 1n claim 1 wherein thehydrogenation is carried out in the presa. closed cycle.

'ence of a. catalyst comprising molybdenum and the hydrogen 1s employedrepeatedly in 3. A process as defined in claim 1 wherein brown coal taris destructively hydrogenated in five vessels arranged in series, thetemperature in the first two vessels being between 410 and 430 C. and inthe others between 430 C. and 460 C.

In testimony whereof I have hereunto set my hand. v

MATHIAS PIER.

